CN111108414B - Optical article and optical filter comprising the same - Google Patents
Optical article and optical filter comprising the same Download PDFInfo
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- CN111108414B CN111108414B CN201880060716.7A CN201880060716A CN111108414B CN 111108414 B CN111108414 B CN 111108414B CN 201880060716 A CN201880060716 A CN 201880060716A CN 111108414 B CN111108414 B CN 111108414B
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/226—Glass filters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
- C09B67/0085—Non common dispersing agents
- C09B67/009—Non common dispersing agents polymeric dispersing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
- G03B11/00—Filters or other obturators specially adapted for photographic purposes
Abstract
The present invention relates to an optical article, an optical filter including the optical article, and an imaging device, the optical article including: a near-infrared-absorbing glass substrate containing divalent copper ions as a coloring component; and a pigment dispersion layer formed on one or both surfaces of the near-infrared ray absorption glass substrate, wherein the near-infrared ray absorption pigment and the ultraviolet ray absorption pigment are dispersed in the resin matrix, and the optical article has a first transmission blocking zone and a second transmission blocking zone, thereby having an advantage that an excellent near-infrared ray cut filter which can effectively block light in the near-infrared ray and ultraviolet ray regions and does not have a difference in color tone due to a change in incident angle can be manufactured.
Description
Technical Field
The present invention relates to an optical article and an optical filter including the same, and particularly to an optical article and an optical filter including the same, which suppress transmission of light in the near infrared and ultraviolet wavelength regions and can significantly reduce short-wavelength shift of a visible light transmittance curve due to an increase in an incident angle.
Background
In order to obtain an Image showing a natural color seen by human eyes, an imaging device using a solid-state imaging element such as a CIS (CMOS Image Sensor) needs an optical member that blocks light in a range of 700nm to 1200nm in a near infrared region detected by a Sensor and transmits light in a range of 400nm to 600nm in a visible light region so as to approximately correct the visibility of human.
Such optical members include a reflection-type near-infrared cut filter in which dielectric multilayer films are formed on both surfaces of ordinary optical glass, and an absorption-type near-infrared cut filter in which a near-infrared absorbing glass containing divalent copper ions as a coloring component is used as a substrate instead of ordinary optical glass and an electrolyte multilayer film is formed on both surfaces thereof. However, in the case of the reflective near infrared cut filter used in the related art, as the incident angle of the light source increases, the spectral transmittance curve in the visible light region shifts to the short wavelength side (hereinafter, referred to as "short wavelength shift"), and there is a problem that a difference in color sensation (or color temperature) is caused greatly depending on the position on a photographed image, and there is a limitation that it cannot be applied to a high-pixel camera module (for example, 5 megapixels or more).
In addition, in the case of the conventional absorption-type near infrared ray cut filter, since the near infrared ray absorbing glass itself is not sufficient to block ultraviolet rays and near infrared ray wavelengths in the range of 700nm to 1200nm, light in the ultraviolet ray and near infrared ray regions is further blocked by forming a dielectric multilayer film on both surfaces of the near infrared ray absorbing glass substrate.
However, with the recent increase in the introduction of wide-angle lenses, the incident angle range of incident light when capturing an image becomes wider, and a problem that a difference in color tone also occurs in the absorption-type near infrared ray cut filter begins to arise. Such a color difference is caused by a short wavelength shift of a visible light transmittance curve of the near infrared ray cut filter in a high pixel camera module to which a wide incident angle is applied.
Therefore, there is a strong demand for development of an optical member that is free from a difference in color when applied to a high-pixel camera module and can effectively block light in the near infrared region and the ultraviolet region.
Disclosure of Invention
Problems to be solved
The invention aims to provide an optical article which has excellent transmittance for light with a wavelength in a visible light region, can effectively block light in a near infrared region and an ultraviolet region, and does not cause color difference along with the change of an incident angle.
It is another object of the invention to provide an optical filter comprising said optical article.
It is a further object of the invention to provide a camera comprising said optical article.
Means for solving the problems
The present applicant and others have developed an optical article formed with a transmission-blocking band that is strictly controlled such that spectral transmittance has a value of a predetermined transmittance or less in a near infrared region and an ultraviolet region and has a predetermined wavelength width, by improving a conventional near infrared ray absorbing glass substrate to have a predetermined spectral characteristic while providing a pigment dispersion layer on one or both sides of the substrate, and have found that a change in an integrated value (area) of the spectral transmittance in a predetermined visible light wavelength region can be controlled to 1% or less even if an incident angle is increased to 40 degrees, thereby enabling to obtain a high-quality image without a difference in color sensation on a photographed image, thereby completing the present invention.
In order to solve the objects of the present invention as described,
the invention provides in one embodiment an optical article comprising:
a near-infrared ray absorption glass substrate containing divalent copper ions as a coloring component, having an average transmittance of 90% or more in a wavelength region of 430nm to 565nm, and having a shortest wavelength (Cut-off T50%) at which the transmittance reaches 50% in a wavelength region having a wavelength longer than 565nm, appearing in 660nm to 690 nm; and
a pigment dispersion layer formed on one or both surfaces of the near-infrared-absorbing glass substrate, in which a near-infrared-absorbing pigment and an ultraviolet-absorbing pigment are dispersed in a resin matrix,
when the transmittance curve of the optical article is measured at an incident angle of 0 degree using a spectrophotometer in a wavelength range of 300nm to 1200nm, the optical article has a first transmittance blocking band having a transmittance of 1% or less in a wavelength region of 690nm to 730nm and a second transmittance blocking band having a transmittance of 25% or less in a wavelength region of 360nm to 410nm,
the optical article satisfies the following conditions (a) to (B):
(A) a wavelength width (W1) of the first transmission rejection band is 5nm to 25 nm;
(B) the second transmission-blocking band has a wavelength width (W2) of 5nm to 45 nm.
In addition, the present invention provides in one embodiment an optical filter including the optical article and a photographing device.
Effects of the invention
The optical article according to the present invention has an advantage of providing an excellent near-infrared cut filter which exhibits high transmittance for light having a wavelength in the visible light region, effectively blocks light in the near-infrared and ultraviolet regions, and is free from a difference in color tone due to a change in incident angle, by comprising a near-infrared absorbing glass substrate and a pigment dispersion layer in which a near-infrared absorbing pigment and an ultraviolet absorbing pigment are dispersed on one surface or both surfaces of the near-infrared absorbing glass substrate.
Drawings
Fig. 1 is a sectional view showing the structure of an optical article to which the present invention relates in one embodiment.
Fig. 2 is a sectional view showing the structure of an optical filter according to the present invention in another embodiment.
Fig. 3 is a graph showing a transmittance curve for the near infrared ray absorption glass substrate.
Fig. 4 is a graph showing absorbance curves for the preparation examples and the comparative preparation examples.
Fig. 5 and 6 are graphs showing the spectral transmittance of the first wavelength selective reflective layer and the second wavelength selective reflective layer, respectively, according to an embodiment of the present invention.
Fig. 7 to 10 are graphs showing spectral transmittances measured for optical articles prepared in production example 3, production example 6, comparative production example 7, and comparative production example 19, respectively, in a wavelength range of 300nm to 1200 nm.
Fig. 11 to 14 are graphs showing spectral transmittances measured for the optical filters prepared in example 3, example 6, comparative example 7, and comparative example 19 in the wavelength range of 300nm to 1200nm, respectively.
Detailed Description
While the invention is susceptible to various modifications and alternative embodiments, specific embodiments have been shown in the drawings and have been described in detail herein.
However, the present invention is not limited to the specific embodiments, and should be understood to include all modifications, equivalents, and alternatives included within the spirit and scope of the present invention.
In the present invention, it should be understood that the terms "comprises," "comprising," "includes," "having," "has," "consisting of … …," or "consisting of … …" are intended to indicate the presence of the stated features, integers, steps, operations or actions, elements, components, or combinations thereof, and do not preclude the presence or addition of one or more other features, integers, steps, operations or actions, elements, components, or combinations thereof.
In addition, it should be understood that the drawings in the present invention are illustrated as being enlarged or reduced for convenience of description.
Hereinafter, the present invention will be described in detail with reference to the accompanying drawings, and the same or corresponding constituent elements are denoted by the same reference numerals regardless of the reference numerals and repeated description thereof will be omitted.
In the present invention, "visible light" is light in a wavelength region that can be perceived by the human eye in electromagnetic waves, and means light in a wavelength range of about 400nm to 700 nm.
In the present invention, "near infrared ray" is an electromagnetic wave located outside the end of red line and having a wavelength longer than visible light, and means light in a wavelength range of about 700nm to 1200 nm. In the present invention, the degree of blocking of the "near infrared ray" can be expressed by absorbance against the near infrared ray.
In the present invention, "ultraviolet rays" are electromagnetic waves that are located outside the end of the blue line and have a wavelength shorter than visible light, and refer to light in a wavelength range of about 300nm to 400 nm. In the present invention, the degree of blocking of the "ultraviolet rays" can be expressed by absorbance against ultraviolet rays.
At this time, the absorbance (OD) is defined as a value obtained by performing a common logarithm on Io/I when the intensity of incident light when light passes through a light absorbing medium is Io and the intensity of the passed light is I. That is, the value represented by the absorbance (OD) log (Io/I) is meant. The absorbance can be calculated using a spectrophotometer.
In the present invention, the "maximum absorption wavelength" refers to a wavelength at which the absorbance is maximum in an absorption spectrum measured by a spectrophotometer in a wavelength range of 300nm to 1200nm for a sample prepared by dissolving a near infrared ray absorbing dye or an ultraviolet ray absorbing dye in cyclohexanone.
In the present invention, the "first transmission stop band" means a wavelength range in which a transmittance is 1% or less in a wavelength region of 690nm to 730nm, and the "second transmission stop band" means a wavelength range in which a transmittance is 25% or less in a wavelength region of 360nm to 410 nm.
In the present invention, "the wavelength width of the first transmission suppression band (W1)" is a value obtained by subtracting the lower limit value of the wavelength from the upper limit value of the wavelength of the first transmission suppression band, and "the wavelength width of the second transmission suppression band (W2)" is a value obtained by subtracting the lower limit value of the wavelength from the upper limit value of the wavelength of the second transmission suppression band.
In the present invention, the "average transmittance" refers to an arithmetic average of transmittance in a predetermined wavelength range in a transmittance curve with wavelength when measuring the transmission spectrum of a near infrared ray absorbing glass substrate, an optical article, an optical filter, and the like with a spectrophotometer.
In addition, in the present invention, the "incident angle" refers to an angle between a light source and a direction perpendicular to a main surface of an optical article or an optical filter when a transmission spectrum or an absorption spectrum of a near infrared ray absorbing glass substrate, the optical article, the optical filter, and the like is measured by a spectrophotometer, and unless otherwise specified, the incident angle refers to an angle measured under a condition of 0 °.
Further, in the present invention, "alkyl group" means a substituent derived from a saturated hydrocarbon in a linear form or a branched form.
In this case, examples of the "alkyl group" include methyl (methyl group), ethyl (ethyl group), n-propyl (n-propyl group), isopropyl (iso-propyl group), n-butyl (n-butyl group), isobutyl (iso-butyl group), sec-butyl (sec-butyl group), tert-butyl (tert-butyl group), n-pentyl (n-pentyl group), 1-dimethylpropyl (1,1-dimethylpropyl group), 1,2-dimethylpropyl (1,2-dimethylpropyl group), 2-dimethylpropyl (2,2-dimethylpropyl group), 1-ethylpropyl (1-ethylpropyl group), 2-ethylpropyl (2-ethylpropyl group), n-hexyl (n-hexyl group), and 1-ethylpropyl (1-ethylpropyl group), 2-ethylpropyl (2-ethylpropyl group), n-hexyl (n-butyl group), n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-dimethylpropyl group, 2-isopropyl group, 2-butyl group, 2-ethyl group, 2-butyl group, 2-ethyl group, 2-butyl group, and the like, 1-ethyl-2-methylpropyl (1-ethyl-2-methylpropyl group), 1,2-trimethylpropyl (1,1,2-trimethylpropyl group), 1-propylpropyl (1-propylpropyl group), 1-methylbutyl (1-methylbutyl group), 2-methylbutyl (2-methylbutyl group), 1-dimethylbutyl (1,1-dimethylbutyl group), 1,2-dimethylbutyl (1,2-dimethylbutyl group), 2-dimethylbutyl (2,2-dimethylbutyl group), 1,3-dimethylbutyl (1,3-dimethylbutyl group), 2,3-dimethylbutyl (2,3-dimethylbutyl group), 2-ethylbutyl (2-ethylbutyl group), 2-methylpentyl (2-methylpentyl group), 2-propylpropyl (1-methylbutyl group), 1-methylbutyl group, 2-dimethylbutyl group, 2-ethylbutyl (2-ethylpentyl group), 2-methylpentyl (2-methylpentyl group), 2-methylbutyl group (2-methylpentyl group), 2-methylbutyl group (1,2-dimethylbutyl group), 2-dimethylpropyl group, 1, 2-methylbutyl group, 2-methylbutyl group, 2-methylbutyl group, 2-methylbutyl group, 2-2, 2-dimethylbutyl group, 2-methylbutyl group, 2, and/2, and/or, 2, 3-methylpentyl (3-methylpentyl group), and the like.
In addition, the "alkyl group" may have a carbon number of 1 to 20, for example, a carbon number of 1 to 12, a carbon number of 1 to 6, or a carbon number of 1 to 4.
Further, in the present invention, "cycloalkyl" means a substituent derived from monocyclic (monocyclic) saturated hydrocarbon.
Examples of the "cycloalkyl group" include cyclopropyl (cyclopropyl group), cyclobutyl (cyclobutyl group), cyclopentyl (cyclopentyl group), cyclohexyl (cyclohexyl group), cycloheptyl (cyclohexyl group), and cyclooctyl (cyclooctyl group).
In addition, the "cycloalkyl group" may have a carbon number of 3 to 20, for example, a carbon number of 3 to 12, or a carbon number of 3 to 6.
Further, in the present invention, "aryl group" means a monovalent substituent derived from an aromatic hydrocarbon.
In this case, examples of the "aryl group" include phenyl (phenyl group), naphthyl (naphthyl group), anthryl (anthryl group), phenanthryl (phenyl group), naphthonaphthyl (naphthoyl group), pyrenyl (pyrenyl group), tolyl (tolyl group), biphenyl (biphenyl group), terphenyl (terphenyl group), bornyl (chrysenyl group), spirobifluorenyl (spirobifluorenyl group), fluoranthenyl (fluorenyl group), perylene (perylenyl group), indenyl (indenyl group), azulenyl (azulenyl group), heptenylyl (heptalenyl group), phenalenyl (phenalenyl group), phenanthrenyl (phenalenyl group), and the like.
In addition, the "aryl group" may have 6 to 30 carbon atoms, for example, 6 to 10 carbon atoms, 6 to 14 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms.
Further, in the present invention, "heteroaryl group" means an "aromatic heterocycle" or a "heterocycle" derived from a single ring or a condensed ring. The "heteroaryl group" includes at least one of nitrogen (N), sulfur (S), oxygen (O), phosphorus (P), selenium (Se), and silicon (Si) as a heteroatom, for example, includes one, two, three, or four.
In this case, examples of the "heteroaryl group" include: including pyrrolyl (pyridyl group), pyridinyl (pyridyl group), triazolyl group, tetrazolyl (tetrazolyl group), benzotriazolyl (benzotriazolyl group), pyrazolyl (pyridyl group), imidazolyl (imidazoyl group), benzimidazolyl (benzimidazolyl group), indolyl (indolyl group), indolinyl (indolinyl group), isoindolyl (isoindolyl group), indolizinyl (indolinyl group), purinyl (purinyl group), quinoxalinyl (quinoxalinyl), quinoxalinyl (quinoyl), quinoxalinyl (quinoxalinyl), quinoxalinyl (quinoyl group), quinoxalinyl (quinoyl), quinoyl (quinoyl group), quinoxalinyl (quinoyl group), quinoxalinyl (quinoyl group (quinoxalinyl (quinoyl group), quinoyl group (quinoyl group), quinoxalinyl (quinoyl group), quinoyl group (quinoyl group), quinoxalinyl (quinoyl group), quinoyl group (quinoxalinyl (quinoyl group), quinoxalinyl (quinoyl group (quinoxalinyl group), quinoyl group (e), quinoxalinyl group (quinoyl group (e), quinoyl group, quinoxalinyl group (e), quinoxalinyl group, quinoyl group, quinoxalinyl (e, quinoxalinyl group, quinoyl group, quinoxalinyl (e, quinoxalinyl group, quinoyl group, quinoxalinyl (e, quinoxalinyl (e, quinoyl group, quinoxalinyl (e, quinoyl group, quinoxalinyl group, quinoyl group, quinoxalinyl group, quinoyl group, quinoxalinyl group, quinoyl group, quinoxalinyl group, quinoyl group, nitrogen-containing heteroaryl groups such as acridinyl group (acridinyl group), phenanthridinyl group (phenanthridinyl group), carbazolyl group (carbazolyl group), carbazolinyl group (carbazolinyl group), pyrimidinyl group (pyrimidinyl group), phenanthrolinyl group (phenanthrolinyl group), phenazinyl group (phenazinyl group), imidazopyridinyl group (imidazopyridinyl group), imidazopyrimidinyl group (imidazopyridinyl group), pyrazolopyridinyl group (pyrazopyridinyl group), and the like; sulfur-containing heteroaryl groups including thienyl (thienyl group), benzothienyl (benzothienyl group), dibenzothienyl (dibenzothienyl group), and the like; and oxygen-containing heteroaryl groups such as furyl (furyl group), pyranyl (pyranyl group), cyclopentylpyranyl (cyclopentylpyranyl group), benzofuryl (benzofuryl group), isobenzofuryl (isobenzofuryl group), dibenzofuryl (dibenzofuryl group), benzodioxazolyl (benzodioxole group), and benzotriazolyl (benzotriazolyl group).
Specific examples of the "heteroaryl group" include thiazolyl (thiazolyl group), isothiazolyl (isothiazolyl group), benzothiazolyl (benzothiazolyl group), benzothiadiazolyl (benzothiazolyl group), phenothiazinyl (phenothiazinyl group), isoxazolyl (isoxazolyl group), furazolyl (furazolyl group), phenoxyazinyl (phenoxyazinyl group), oxazolyl (oxazolyl group), benzoxazolyl (benzoxazolyl group), oxadiazolyl (oxydazolyl group), pyrazolooxazolyl (pyrazoloxazolyl group), imidazopyridyl (pyrazoloxazolyl group), imidazothiazolyl (imidazothiazolyl group), thienofuranyl (thiazolooxazolyl group), pyrazolooxazolyl (pyrazolooxazolooxazolyl group), and the like, and at least two of these compounds are included.
Further, the "heteroaryl" group may have a carbon number of 2 to 20, such as 4 to 19, 4 to 15, or 5 to 11. For example, when a heteroatom is included, the heteroaryl group can have a ring member (ring member) of 5 to 21.
In addition, in the present invention, "aralkyl group" means a saturated hydrocarbon substituent to which a monovalent substituent derived from an aromatic hydrocarbon is bonded at a hydrogen position of a terminal hydrocarbon. That is, "aralkyl" refers to an alkyl group having a chain end substituted with an aryl group, and examples thereof include benzyl (benzyl group), phenethyl (phenethyl group), propyl (phenylpropyl group), naphthylmethyl (naphthylmethyl group), naphthylethyl (naphthylethyl group), and the like.
The present invention will be described in detail below.
< optical article >
In one embodiment, the optical article of the present invention comprises: a near-infrared ray absorption glass substrate containing divalent copper ions as a coloring component, having an average transmittance of 90% or more in a wavelength region of 430nm to 565nm, and having a shortest wavelength (Cut-off T50%) at which the transmittance reaches 50% in a wavelength region longer than 565nm, occurring in 660nm to 690 nm; and a dye dispersion layer formed on one or both surfaces of the near-infrared-absorbing glass substrate, wherein the near-infrared-absorbing dye and the ultraviolet-absorbing dye are dispersed in the resin matrix. As an example, the near infrared absorbing dye may have a maximum absorption wavelength in a range of 690nm to 750nm, and the ultraviolet absorbing dye may have a maximum absorption wavelength in a wavelength region of 350nm to 410 nm. The near-infrared absorbing dye or the ultraviolet absorbing dye may be two or more absorbing dyes having maximum absorption wavelengths in the above wavelength range.
In addition, when the transmittance curve of the optical article is measured with a spectrophotometer at an incident angle of 0 degree in a wavelength range of 300nm to 1200nm, the optical article of the present invention has a first transmittance blocking band exhibiting a transmittance of 1% or less in a wavelength region of 690nm to 730nm and a second transmittance blocking band exhibiting a transmittance of 25% or less in a wavelength region of 360nm to 410nm, and satisfies the following conditions (a) to (B):
(A) the first transmission stop band has a wavelength width W1 of 5nm to 25 nm;
(B) the wavelength width W2 of the second transmission stop band is 5nm to 45 nm.
The optical article of the present invention satisfies the conditions (a) to (B), and thus can provide an optical filter that effectively blocks light in the near infrared and ultraviolet regions without hindering the transmittance of light in the visible light region, and that does not cause a difference in color tone due to a short wavelength shift caused by an increase in the incident angle. The wavelength width W1 is preferably 6nm to 24nm, more preferably 8nm to 23 nm. In addition, the wavelength width W2 is preferably 7nm to 43nm, more preferably 9nm to 42 nm.
In addition, in the absorbance curve of the optical article, when the maximum value of absorbance is normalized to 1 in the wavelength region of the first transmission inhibition band, the maximum value OD2 of absorbance in the wavelength region of the second transmission inhibition band may satisfy the condition of the following formula 1.
[ formula 1]
0.2≤OD2≤0.4。
In the present invention, in formula 1, the OD2 value may be in the range of 0.2 to 0.4, 0.21 to 0.39, 0.23 to 0.37, or 0.25 to 0.37. When the OD2 value is less than 0.2, a short wavelength shift of the visible light transmittance curve increases with an increase in incident angle, and thus a difference in color sensation increases, and when the OD2 is greater than 0.4, a decrease in visible light transmittance occurs, and thus it is difficult to obtain a high-quality image when photographed in a low-illuminance environment. The optical article of the present invention satisfies the condition of expression 1, and thus can provide an optical filter that suppresses short-wavelength shift and prevents the occurrence of color difference without hindering the transmittance of light in the visible light region.
Fig. 1 is a sectional view showing the structure of an optical article of the present invention. Referring to fig. 1 (a) and (b), the optical article 10 includes a near-infrared-absorbing glass substrate 13 containing divalent copper ions as a coloring component. The following substrates were used as the near-infrared ray absorbing glass substrate used in the conventional near-infrared ray cut filter: in a wavelength region of 430nm to 565nm, the average transmittance is 90% or less, and in a wavelength region of longer than 565nm, the shortest wavelength (Cut-off T50%) at which the transmittance reaches 50% is 650nm or less. In contrast, in the near-infrared-absorbing glass substrate included in the optical article according to the present invention, it is preferable that the average transmittance in the wavelength range is 90% or more and the Cut-off T50% value has a value in the range of 660nm to 690 nm. The thickness of the near infrared ray absorption glass substrate may be in a range of 0.140mm to 0.220 mm. Preferably, the thickness of the near infrared ray absorption glass substrate may be in the range of 0.145mm to 0.210 mm. The thickness of the near-infrared ray absorbing glass substrate can be controlled within the range to impart a supporting effect to an optical article, and at the same time, predetermined optical characteristics including the average transmittance and Cut-off T50% and the like can be imparted. On one or both surfaces of the near-infrared absorbing glass substrate 13, there are formed pigment dispersion layers 14, 14a, 14b in which the near-infrared absorbing pigment 11 and the ultraviolet absorbing pigment 12 are dispersed in a resin matrix. Fig. 1 (a) shows a structure in which a dye dispersion layer 14 in which a near-infrared absorbing dye 11 and an ultraviolet absorbing dye 12 are dispersed together in a resin is formed on one surface of a near-infrared absorbing glass substrate 13. Fig. 1 (b) shows a structure in which a dye dispersion layer 14a in which the near-infrared absorbing dye 11 is dispersed in a resin is formed on one surface of the near-infrared absorbing glass substrate 13, and a dye dispersion layer 14b in which the ultraviolet absorbing dye 12 is dispersed in a resin is formed on the opposite surface.
The polymer resin constituting the resin matrix may be selected from a range in which the near-infrared absorbing dye and the ultraviolet absorbing dye are easily dispersed and do not inhibit optical characteristics. The polymer resin may include, for example, one or more selected from the group consisting of polyester resins, polycarbonate resins, acrylic resins, polyolefin resins, cycloolefin resins, polyimide resins, polyamide resins, and polyurethane resins.
The optical article according to the present invention includes the near-infrared-absorbing glass substrate 13 having the above-described optical characteristics and the pigment dispersion layers 14, 14a, and 14b, and thus can provide an optical filter that is compatible with a general-purpose image sensor and does not cause a difference in color tone. In one embodiment, the near infrared absorbing dye 11 may have a maximum absorption wavelength in a range of 690nm to 750nm, and the ultraviolet absorbing dye 12 may have a maximum absorption wavelength in a wavelength region of 350nm to 410 nm. Preferably, the near-infrared absorbing dye 11 may have a maximum absorption wavelength in a range of 700nm to 750nm, and the ultraviolet absorbing dye 12 may have a maximum absorption wavelength in a wavelength region of 370nm to 400 nm.
The near-infrared absorbing dye 11 may be, for example, a cyanine compound, a phthalocyanine compound, a naphthalocyanine compound, a porphyrin compound, a benzoporphyrin compound, an indole compound, a triazine compound, a benzotriazole compound, a squalin compound, an anthraquinone compound, a croconic acid (croconium) compound, a diimmonium-based compound, and/or a dithiol metal complex. As an example, the near infrared absorbing dye 11 may be represented by the following chemical formula 1.
[ chemical formula 1]
In the chemical formula 1, the metal oxide is represented by,
a represents an aminophenyl group; an indole methylene group; or an indolinyl group, or a pharmaceutically acceptable salt thereof,
has two A to
Are combined with each other as a centerIn combination with (coupling) the structure,
any one or more of hydrogen atoms present in the aminophenyl, indolylmethylene or indolinyl group represents, independently of one another, hydrogen, halogen, hydroxyl, cyano, nitro, carboxyl, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a sulfonamide group, or an amide group which is substituted or unsubstituted with an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms;
specifically, the chemical formula 1 may be any one of the compounds represented by the following chemical formulas 1a to 1 c.
[ chemical formula 1a ]
[ chemical formula 1b ]
[ chemical formula 1c ]
In the chemical formulas 1a to 1c,
a1、a2and a3Independently of one another, hydrogen, halogen, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a sulfonamide group, or an amide group which is substituted or unsubstituted with an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
< coloring matter for ultraviolet absorption >
The ultraviolet absorbing dye 12 may be represented by the following chemical formula 2.
[ chemical formula 2]
R1To R3Each independently represented by hydrogen, cyano group, amino group or the following chemical formula 2-a,
[ chemical formula 2-a ]
In the chemical formula 2-a, the metal oxide,
b1each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms,
R4represents hydrogen, cyano or represented by the following chemical formula 2-b,
[ chemical formula 2-b ]
In the chemical formula 2-b, the metal oxide,
b2represents hydrogen, an alkyl group having 1 to 18 carbon atoms, or an amino group.
R of the chemical formula 21To R4Wherein each of the hydrogen atoms of (a) is independently substituted or unsubstituted with one member selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, a halogen, a cyano group, a nitro group, a hydroxyl group and a carboxyl group.
The total content of the near infrared absorbing pigment 11 and the ultraviolet absorbing pigment 12 may be in the range of 2.5 to 5.5 parts by weight, specifically 2.6 to 5.0 parts by weight, 2.8 to 4.5 parts by weight, or 2.9 to 4.0 parts by weight, relative to 100 parts by weight of the pigment dispersion layers 14, 14a, 14 b. In addition, the content ratio of the ultraviolet absorbing dye 12 to the near infrared absorbing dye 11 may be in the range of 0.5 to 3.0, specifically, 0.6 to 2.9, 1.0 to 2.8, or 1.2 to 2.7 by weight ratio.
The optical article of the present invention includes the pigment dispersion layers 14, 14a, 14b, and the pigment dispersion layers 14, 14a, 14b contain the near infrared absorbing pigment 11 and the ultraviolet absorbing pigment 12 having the maximum absorption wavelength in the wavelength range in the predetermined content and content ratio among the various types and forms of pigments, whereby it is possible to suppress short-wavelength shift of the visible light transmittance curve without causing color difference, and at the same time, to provide high transmittance in the visible light region, and to realize an optical filter capable of providing a brighter image at the time of image capturing.
In another embodiment, the present invention relates to an optical article in which the longest wavelength (λ _ cut-on) at which the transmittance reaches 50% in a wavelength region of 430nm or less may exist in a wavelength region of 410nm to 420nm, and the shortest wavelength (λ _ cut-off) at which the transmittance reaches 50% in a wavelength region of 565nm or more may exist in a wavelength region of 625nm to 645 nm. The λ _ cut-on value and the λ _ cut-off value exist in the predetermined wavelength range, and therefore, when used in combination with a commonly used image sensor, a high-quality image that sufficiently reproduces colors inherent to the subject can be obtained. When the λ _ cut-on value is smaller than the value of the range, blue may be over-emphasized, or when the λ _ cut-on value is larger than the value of the range, blue feeling may be insufficient. In addition, when the λ _ cut-off value is smaller than the value of the range, the red feeling may be insufficient, or when the λ _ cut-off value is larger than the value of the range, an image in which the red color is excessively emphasized may be obtained.
In addition, the optical article is characterized in that the average transmittance is 87% or more in a wavelength region of 430nm to 565 nm. In the case where the average transmittance is less than 87%, there is a problem that the shape of the object cannot be clearly reproduced when an image is captured in a low illuminance environment.
Additionally, in one embodiment, the optical article may have an average transmittance of 25% or more over a wavelength region of 800nm to 1200nm and a transmittance of 50% or more at 1200 nm. Specifically, the optical article may have an average transmittance of 26% or more, 29% or more, or 32% or more in a wavelength region of 800nm to 1200nm, and a transmittance of 51% or more or 55% or more at a wavelength of 1200 nm. The optical article of the present invention can form the first transmission preventing tape for light in a wavelength region of 700nm to 750nm affecting an image of a photographing device to perform effective blocking. However, light in a wavelength region of 750nm or more is selectively blocked by transmitting light at a predetermined level and forming a selective wavelength reflection layer on one or both surfaces of the optical article, thereby selectively blocking light in a wavelength region of 400nm or less and/or a wavelength region of 750nm or more. Thus, when the optical article according to the present invention is applied to an imaging device, it is possible to obtain a bright image by the imaging device by providing a high transmittance in the visible light region while suppressing the occurrence of a difference in color tone due to an increase in the incident angle.
In addition, the optical article can effectively reduce the phenomenon of the angle shift of the transmission spectrum with the incident light. In one embodiment, the optical article may have an absolute value of a difference between a wavelength at which a transmittance of 30% at an incident angle of 0 degrees (λ _ T30% @0 °) and a wavelength at which a transmittance of 30% at an incident angle of 40 degrees (λ _ T30% @40 °), in a wavelength region of 400nm to 410nm, of 5nm or less, 3nm or less, or substantially 2nm or less. Thus, the optical article according to the present invention can suppress short-wavelength shift of the transmittance curve in the visible light region with an increase in the incident angle of light, and can suppress a change in the integrated value (area) of the transmittance in the visible light region to 1% or less, thereby providing an optical filter that can significantly reduce a change in color tone due to an increase in the incident angle.
< optical Filter >
In addition, the present invention provides an optical filter including the aforementioned optical article.
The optical filter may be a structure including a wavelength selective reflective layer formed on one or both sides of an optical article. Thus, when the optical filter measures a transmission spectrum with a spectrophotometer in a wavelength range of 300nm to 1200nm under the condition of an incident angle of 0 degree, the following conditions (i) and (ii) can be satisfied:
(i) a shortest wavelength (λ _ cut-off) at which transmittance reaches 50% in a wavelength region longer than a wavelength of 565nm is in a range of 630nm to 655 nm;
(ii) the average transmittance is 93% or more in a wavelength region of 430nm to 565 nm.
This means that the optical filter according to the present invention can be used in combination with a general-purpose image sensor, and exhibits high transmittance for light having a wavelength in the visible light region, thereby providing a clear and bright image even in a low-illuminance imaging environment.
The optical filter according to the present invention is an optical filter in which a selective wavelength reflecting layer is formed on one or both surfaces of an optical article, thereby reflecting light in a predetermined wavelength region that is not blocked by absorption to selectively block the light. For example, near-infrared light in a wavelength region of 700nm or more and ultraviolet light in a wavelength region of 400nm or less can be selectively blocked.
The λ cut-off may preferably be in the range of 632nm to 653nm, and may more preferably be in the range of 635nm to 650 nm. The average transmittance may be preferably 93.5% or more, and more preferably 94% or more.
In one embodiment, the optical filter satisfies the following formula 2:
[ formula 2]
|(A-B)/A|*100≤1％。
In the formula 2, A represents an integrated value of the transmittance when a transmittance curve of the optical filter is measured at an incident angle of 0 degree using a spectrophotometer in a wavelength range of 380nm to 780nm,
b represents an integrated value of the transmittance when the transmittance curve of the optical filter is measured at an incident angle of 40 degrees using spectrophotometry in a wavelength range of 380nm to 780 nm. The integrated value of the transmittance is a factor related to the amount of light reaching the image sensor, and it is preferable that the change in the integrated value is small regardless of the change in the incident angle.
The optical filter according to the present invention can effectively suppress short-wavelength shift of a visible light transmittance curve even when the incident angle of incident light increases to 40 degrees, thereby preventing occurrence of color difference. For example, as shown in the above equation 2, the difference between the transmittance for light incident under the condition of an incident angle of 0 degree and the integrated value of the transmittance for light incident under the condition of an incident angle of 40 degrees may be 1% or less, preferably 0.5% or less, and more preferably 0.2% or less.
Fig. 2 is a sectional view showing the structure of an optical filter to which the present invention relates in one embodiment. Referring to fig. 2, the optical filter of the present invention includes an optical article 10 and wavelength selective reflecting layers 20 and 30 on both surfaces of the optical article 10, and the optical article 10 includes a near-infrared ray absorbing glass substrate 13 and pigment dispersing layers 14, 14a, and 14b in which a near-infrared ray absorbing pigment and/or an ultraviolet ray absorbing pigment are dispersed on one surface or both surfaces of the near-infrared ray absorbing glass substrate 13.
Since the near-infrared-absorbing glass substrate 13, the pigment dispersion layers 14, 14a, and 14b, and the optical article 10 have been described above, redundant description is omitted.
In the optical filter of the present invention, the selective wavelength reflection layers 20 and 30 may selectively reflect light of a predetermined wavelength range among light incident to the optical filter, or may provide a function of an anti-reflection layer for preventing reflection in order to increase transmission of light in a visible light region. For example, a case where light having a wavelength in the range of 700nm to 1200nm and a wavelength in the range of 300nm to 400nm is reflected while blocking the incidence of the light of the ranges to the image sensor, and a case where light of a visible light region in the wavelength range of 400nm to 700nm is prevented from being reflected, whereby an effect of increasing the light amount of the light of the wavelength range which is incident to the image sensor can be performed. That is, the wavelength-selective reflection layers 20 and 30 may perform the functions of a near infrared ray reflection layer that reflects near infrared rays, an ultraviolet ray reflection layer that reflects ultraviolet rays, and/or a reflection preventing layer that prevents visible light from being reflected.
In one embodiment, the optical filter may include a first wavelength selective reflective layer 20 formed on a first major face of the optical article and a second wavelength selective reflective layer 30 formed on a second major face of the optical article. The first selective wavelength reflection layer 20 may perform an anti-reflection function of an anti-reflection layer in a wide wavelength region including a visible light region, a partial ultraviolet region having a wavelength shorter than a short wavelength end of the visible light region, and a partial near infrared region having a wavelength longer than a long wavelength end of the visible light region, and the second selective wavelength reflection layer 30 may perform a function of transmitting light in the visible light region with a high transmittance of 95% or more and selectively reflecting light in the ultraviolet region and the near infrared region. In contrast, the first selective wavelength reflection layer 20 may perform an effect of selectively reflecting light of an ultraviolet region, and the second selective wavelength reflection layer 30 may perform an effect of selectively reflecting light of a near infrared region. In the above description, the first selective wavelength reflection layer and the second selective wavelength reflection layer that perform the respective functions are provided on the first main surface and the second main surface, respectively, but the second selective wavelength reflection layer 30 may be provided on the first main surface and the first selective wavelength reflection layer 20 may be provided on the second main surface.
As an example, the selective wavelength reflection layers 20 and 30 may have a structure of a dielectric multilayer film in which high refractive index layers and low refractive index layers are alternately stacked, and may further include an aluminum deposited film, a noble metal thin film, or a resin film in which fine particles of one or more of indium oxide and tin oxide are dispersed. For example, the selective wavelength reflection layers 20 and 30 may have a structure in which dielectric layers (not shown) having a first refractive index and dielectric layers (not shown) having a second refractive index are alternately stacked, and a difference between the refractive indices of the dielectric layers having the first refractive index and the dielectric layers having the second refractive index may be 0.2 or more, 0.3 or more, or 0.2 to 1.0.
In addition, the high refractive index layer and the low refractive index layer of the wavelength selective reflection layers 20 and 30 are not particularly limited as long as the high refractive index layer and the low refractive index layerThe difference in refractive index of the layers is included in the aforementioned range, but specifically, the high refractive index layer may include one or more selected from the group consisting of titanium oxide, aluminum oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc sulfide, and indium oxide having a refractive index of 1.6 to 2.4, and the indium oxide may further contain titanium oxide, tin oxide, cerium oxide, or the like in a small amount. In addition, the low refractive index layer may include a material selected from the group consisting of silicon dioxide, lanthanum fluoride, magnesium fluoride, and sodium hexafluoroaluminate (cryolite, Na) having a refractive index of 1.3 to 1.63AlF6) One or more of the group consisting of.
As described above, the optical filter according to the present invention can limit the range of transmitted light to the visible light region, and when the optical filter is applied to an imaging device, it is possible to realize bright and sufficient reproduction of an image of a primary color without causing a difference in color tone when the incident angle increases.
< imaging apparatus >
Further, the present invention provides in one embodiment a photographing apparatus including the optical filter.
The imaging device according to the present invention includes the above-described optical filter, and exhibits high transmittance for light having a wavelength in the visible light region. Further, since the optical filter is provided which has a high average transmittance of 93% or more in the visible light region even when the incident angle of the light source is increased to 40 degrees and suppresses a short-wavelength shift of the visible light transmittance curve, a difference in color tone is not caused in accordance with a change in position in an image captured by the imaging device, and a bright and sufficient primary color image can be reproduced.
Therefore, the imaging element can be effectively used in electronic devices to which the imaging device is applied, such as a digital CAMERA, a portable CAMERA, a digital video CAMERA, a personal CAMERA (PC CAMERA), a surveillance CAMERA, a vehicle-mounted CAMERA, a portable information terminal, a personal computer, a video game, a medical device, a USB memory, a portable game machine, a fingerprint authentication system, and a digital music player.
The present invention will be described in detail below with reference to preparation examples, examples and experimental examples.
However, the following preparation examples, examples and experimental examples merely illustrate the present invention, and the contents of the present invention are not limited to the following preparation examples, examples and experimental examples.
The near-infrared-absorbing glass substrates 13 used in the preparation examples and comparative preparation examples, examples and comparative examples were prepared by grinding commercially available BG61 (trade name, Schott, germany). Each of the near-infrared ray absorption glass substrates having different thicknesses was prepared by changing the polishing thickness, and the thickness thereof was measured. Specifically, for a near infrared ray absorption glass substrate having a length of 77mm in each of the lateral and longitudinal directions, a total of five positions including a central portion and four positions distant from the central portion by 50mm in the diagonal direction were measured using a high-precision micrometer (Mitutoyo Co., Ltd., trade name: MDH-25M), and the arithmetic average of the thicknesses of the five positions was taken as its thickness. As shown in Table 1, the thickness of the near infrared ray absorption glass substrate was 0.145mm, 0.165mm, 0.190mm and 0.210mm, respectively.
The optical characteristics of the near-infrared ray absorbing glass substrate were investigated. Specifically, for each near-infrared ray absorption glass substrate, the transmittance for a wavelength range of 300nm to 1200nm was measured using a spectrophotometer (Perkinelmer, trade name: LAMBDA 750). From the measurement results, the average transmittance of visible light in the wavelength range of 430nm to 565nm and the shortest wavelength (Cut-off T50%) at which the transmittance reaches 50% in the wavelength region having a wavelength longer than 565nm were calculated and are shown together in Table 1. Meanwhile, fig. 3 shows a transmittance curve for the near-infrared ray absorption glass substrate disclosed in table 1 below.
[ Table 1]
| Thickness [ mm ]] | 0.145 | 0.165 | 0.190 | 0.210 |
| Average visible light transmittance [% ]] | 90.7 | 90.5 | 90.3 | 90.1 |
| Cut-off T50％[nm] | 690.0 | 679.4 | 668.9 | 662.0 |
As is clear from the results in Table 1, it is possible to ensure optical characteristics such that the average visible light transmittance is 90% or more and the Cut-off T50% wavelength is 660nm to 690nm by using a near-infrared absorbing glass having a thickness of 0.140mm to 0.220mm and containing divalent copper ions.
Preparation examples 1 to 6
As a production example relating to the present invention, an optical article having a first transmission-blocking tape and a second transmission-blocking tape was prepared in the following manner.
A near infrared ray absorbing pigment N1(h.w. sands corp., usa) represented by chemical formula 1 and having a maximum absorption wavelength in a wavelength range of 710 ± 5nm, a near infrared ray absorbing pigment N2(h.w. sands corp., usa) represented by chemical formula 1 and having a maximum absorption wavelength in a wavelength range of 740 ± 5nm, and an ultraviolet ray absorbing pigment U1(h.w. sands corp., usa) represented by chemical formula 2 and having a maximum absorption wavelength in a wavelength range of 380 ± 5nm were mixed in the following content of table 2 based on 100 parts by weight of the resin. In this case, polymethyl methacrylate (PMMA) resin is used as the resin, and cyclohexanone (cyclohexenone) is used as the organic solvent. Thereafter, the mixture was stirred with a stirrer for 24 hours or more to prepare an absorbing solution. The prepared absorbing solution was coated on a cross section of the near infrared ray absorbing glass substrate of table 1 having a thickness of 0.145mm and cured for 160 to 120 minutes, thereby preparing an optical article having a color element dispersion layer formed on the cross section as shown in (a) of fig. 1.
[ Table 2]
For each of the optical articles prepared according to preparation examples 1 to 6 to which the present invention relates, a transmittance curve and an absorbance curve were measured at an incident angle of 0 degree using a spectrophotometer in a wavelength range of 300nm to 1200 nm. From the measured results, the wavelength width W1 of the first transmittance band exhibiting a transmittance of 1% or less at 565nm or more and the wavelength width W2 of the second transmittance band exhibiting a transmittance of 25% or less at 430nm or less were calculated. In addition, a maximum value OD2 of absorbance of the second transmission inhibition band was calculated when the absorbance curve was normalized so that the maximum value OD1 of absorbance of the first transmission inhibition band became 1. The results are shown together in said table 2. Further, an absorbance curve for each of the optical articles according to preparation examples 3 and 6 disclosed in the table 2 is shown in fig. 4. Referring to table 2 and fig. 4, it is understood that when the total content of the near infrared ray absorbing pigments N1 and N2 and the ultraviolet ray absorbing pigment U1 (N1+ N2+ U1) is set to a range of 3.12 to 4.49 parts by weight, and the contents of N1, N2 and U1 are changed so that the content ratio of the ultraviolet ray absorbing pigment to the near infrared ray absorbing pigment (U1/(N1+ N2)) becomes a range of 0.99 to 2.19 weight ratio, the wavelength width W1 of the first transmission suppression band can be adjusted to a range of 8.3nm to 20.5nm with the adjustment of the contents of N1 and N2, and the wavelength width W2 of the second transmission suppression band can be adjusted to a range of 10.3nm to 41.9nm with the adjustment of the content of U1. Further, it was found that the OD2 value could be adjusted to a range of 0.25 to 0.37 as the content ratio of the ultraviolet absorbing dye to the total content of the near-infrared absorbing dye was adjusted.
Preparation examples 7 to 12
Optical articles of production examples 7 to 12 were prepared by substantially the same method as that of production examples 1 to 6, except that the contents of the near-infrared ray absorbing glass substrate having a thickness of 0.165mm and the near-infrared ray absorbing pigment N1 having a maximum absorption wavelength at 710 ± 5nm, the near-infrared ray absorbing pigment N2 having a maximum absorption wavelength at 740 ± 5nm, and the ultraviolet ray absorbing pigment U1 having a maximum absorption wavelength at 380 ± 5nm of table 1 were used. In this case, the contents of the near infrared absorbing dye and the ultraviolet absorbing dye are shown in table 3 below.
[ Table 3]
The wavelength widths W1 of the first transmission inhibition band, the wavelength widths W2 of the second transmission inhibition band, and the absorbance values of the optical articles according to production examples 7 to 12 were calculated by methods substantially the same as the methods for measuring the transmittance and absorbance of the optical articles according to production examples 1 to 6. The results are shown in said table 3. Referring to table 3, in the case where the total content (N1+ N2+ U1) of the near infrared ray absorbing pigments N1 and N2 and the ultraviolet ray absorbing pigment U1 was set to be in the range of 3.05 to 4.35 parts by weight, and the content of N1, N2 and U1 was changed so that the content ratio (U1/(N1+ N2)) of the ultraviolet ray absorbing pigment to the near infrared ray absorbing pigment became in the range of the weight ratio of 1.06 to 2.34, it was found that the wavelength width W1 of the first transmission-stop band could be adjusted to the range of 8.6nm to 21.3nm with the adjustment of the content of N1 and N2, and the wavelength width W2 of the second transmission-stop band could be adjusted to the range of 9.8nm to 40.5nm with the adjustment of the content of U1. Further, it was found that the OD2 value could be adjusted in the range of 0.26 to 0.37 as the content ratio of the ultraviolet absorbing dye to the total content of the near-infrared absorbing dye was adjusted.
Preparation examples 13 to 18
Optical articles according to production examples 13 to 18 were prepared by substantially the same method as that of production examples 1 to 6, except for the contents of the near-infrared ray absorbing glass substrate having a thickness of 0.190mm, the near-infrared ray absorbing pigment N1 having a maximum absorption wavelength at 710 ± 5nm, the near-infrared ray absorbing pigment N2 having a maximum absorption wavelength at 740 ± 5nm, and the ultraviolet ray absorbing pigment U1 having a maximum absorption wavelength at 380 ± 5nm in table 1. In this case, the contents of the near-infrared absorbing dye and the ultraviolet absorbing dye are shown in table 4 below.
[ Table 4]
The wavelength widths W1 of the first transmission inhibition band, the wavelength widths W2 of the second transmission inhibition band, and the absorbance values of the optical articles according to production examples 13 to 18 were calculated by methods substantially the same as the described methods for measuring the transmittance and absorbance of the optical articles according to production examples 1 to 6. The results are shown in said table 4. Referring to table 4, in the case where the total content (N1+ N2+ U1) of the near infrared absorbing pigments N1 and N2 and the ultraviolet absorbing pigment U1 was set to the range of 3.00 to 4.20 parts by weight, and the content of N1, N2 and U1 was changed so that the content ratio (U1/(N1+ N2)) of the ultraviolet absorbing pigment to the near infrared absorbing pigment was in the range of the weight ratio of 1.12 to 2.30, it was found that the wavelength width W1 of the first transmission-stop band could be adjusted to the range of 10.0nm to 22.3nm as the content of N1 and N2 was adjusted, and the wavelength width W2 of the second transmission-stop band could be adjusted to the range of 9.9nm to 37.1nm as the content of U1 was adjusted. Further, it was found that the OD2 value could be adjusted in the range of 0.26 to 0.34 as the content ratio of the ultraviolet absorbing dye to the total content of the near-infrared absorbing dye was adjusted.
Preparation examples 19 to 24
Optical articles according to production examples 19 to 24 were prepared by substantially the same method as that of production examples 1 to 6, except for the contents of the near-infrared ray absorbing glass substrate having a thickness of 0.210mm, the near-infrared ray absorbing pigment N1 having a maximum absorption wavelength at 710 ± 5nm, the near-infrared ray absorbing pigment N2 having a maximum absorption wavelength at 740 ± 5nm, and the ultraviolet ray absorbing pigment U1 having a maximum absorption wavelength at 380 ± 5nm in table 1. In this case, the contents of the near infrared absorbing dye and the ultraviolet absorbing dye are shown in table 5 below.
[ Table 5]
The wavelength widths W1 of the first transmission inhibition bands, the wavelength widths W2 of the second transmission inhibition bands, and the absorbance values of the optical articles according to production examples 19 to 24 were calculated by substantially the same methods as the methods for measuring the transmittance and absorbance of the optical articles according to production examples 1 to 6. The results are shown in said table 5. Referring to table 5, in the case where the total content (N1+ N2+ U1) of the near infrared ray absorbing pigments N1 and N2 and the ultraviolet ray absorbing pigment U1 was set to be in the range of 2.94 to 3.91 parts by weight, and the content of N1, N2 and U1 was changed so that the content ratio (U1/(N1+ N2)) of the ultraviolet ray absorbing pigment to the near infrared ray absorbing pigment was in the range of 1.25 to 2.63 weight ratio, it was found that the wavelength width W1 of the first transmission stop band could be adjusted to the range of 9.9nm to 20.1nm with the adjustment of the content of N1 and N2, and the wavelength width W2 of the second transmission stop band could be adjusted to the range of 13.8nm to 39.2nm with the adjustment of the content of U1. Further, it was found that the OD2 value could be adjusted in the range of 0.26 to 0.36 as the content ratio of the ultraviolet absorbing dye to the total content of the near-infrared absorbing dye was adjusted.
Examples 1 to 24
SiO was alternately evaporated on the first main surface of the optical article prepared in the preparation examples 1 to 24 at a temperature of 110. + -. 5 ℃ by using an electron beam evaporator (E-beam evaporator)2And Ti3O5A first wavelength selective reflective layer of a dielectric multilayer film structure is formed. Thereafter, at 11Alternately depositing SiO on the second main surface of the optical article by an electron beam evaporator (E-beam evaporator) at a temperature of 0 + -5 DEG C2And Ti3O5The second selective wavelength reflection layer of the dielectric multilayer film structure was formed, thereby preparing the optical filters according to examples 1 to 24 having the structure shown in fig. 2 (a). In this case, the number of stacked layers and the thickness of the stacked first and second wavelength selective reflective layers are shown in table 6 below. Here, the thickness means the total thickness of each of the first wavelength selective reflection layer and the second wavelength selective reflection layer in units of micrometers (μm).
[ Table 6]
In addition, the respective laminated structures and thicknesses of the first wavelength selective reflection layer and the second wavelength selective reflection layer applied to the above-described embodiments 1 to 24 are shown in the following tables 7 and 8, respectively.
[ Table 7]
[ Table 8]
The first selective wavelength reflecting layer according to the present embodiment may be caused to perform the function of an antireflection layer that provides a high average transmittance of 96% or more in the visible light region of 430nm to 565nm and also provides a transmittance of 75% or more in a wide wavelength region including a partial ultraviolet region having a wavelength shorter than the short wavelength end of the visible light region and a partial near infrared region having a wavelength longer than the long wavelength end of the visible light region, and the second selective wavelength reflecting layer may be caused to perform the function of an ultraviolet and near infrared reflecting layer that transmits light in the visible light region at a high average transmittance of 95% or more and selectively reflects light in the ultraviolet region and the near infrared region. In contrast to this, the first selective wavelength reflecting layer may be made to perform an action of selectively reflecting light in the ultraviolet region, and the second selective wavelength reflecting layer may be made to perform an action of selectively reflecting light in the near infrared region. In any case, in order to make full use of the spectral transmittance characteristics of the optical article and apply it to a camera module having a high pixel density, it is necessary to provide a selective wavelength reflection layer on the main surface of the optical article, and it is preferable to provide a selective wavelength reflection layer so as to block light in the ultraviolet region of about 400nm or less and the near infrared region of about 700nm or more to such an extent that defects in image quality are not caused. The spectral transmittances of the first wavelength selective reflective layer disclosed with respect to said table 7 and the second wavelength selective reflective layer disclosed with respect to table 8 are shown in fig. 5 and 6, respectively.
Referring to fig. 6, it is understood that there are transition regions in which the transmittance changes rapidly in the partial wavelength region between the visible light region and the near infrared region (transition region a) and in the partial wavelength region between the ultraviolet region and the visible light region (transition region B). It is also known that a short-wavelength shift phenomenon occurs in which each transition region shifts to the short-wavelength side as the incident angle increases from 0 degrees to 40 degrees, and that a short-wavelength shift of about 39nm occurs in the transition region a and a short-wavelength shift of about 22nm occurs in the transition region B, based on the wavelength at which the transmittance is 50%. Such a short wavelength shift may cause a difference in color tone with an increase in the incident angle of the light source. However, as described above, the optical article according to the present invention can provide an optical filter in which the difference in color tone is substantially suppressed by overlapping the first transmission-blocking zone and the second transmission-blocking zone in the transition regions a and B of the wavelength-selective reflective layer so that the difference in the integrated value of the transmittance with the increase in the incident angle of the visible light transmittance curve is less than 1%.
Comparative preparation examples 1 to 19
Optical articles of comparative production examples 1 to 19 were prepared by substantially the same method as the production examples 1 to 6, except for the contents of the pigment for near infrared absorption N1 having a maximum absorption wavelength at 710 ± 5nm, the pigment for near infrared absorption N2 having a maximum absorption wavelength at 740 ± 5nm, and the pigment for ultraviolet absorption U1 having a maximum absorption wavelength at 380 ± 5 nm. In this case, the contents of the near-infrared absorbing dye and the ultraviolet absorbing dye are shown in table 9 below.
[ Table 9]
The wavelength width W1 of the first transmission inhibition band, the wavelength width W2 of the second transmission inhibition band, and the absorbance value of the optical articles according to comparative preparation examples 1 to 19 were calculated by substantially the same methods as the methods for measuring the transmittance and absorbance of the optical articles according to the preparation examples 1 to 6. The results are shown in Table 9. Fig. 4 also shows the absorbance curves of the optical articles according to comparative preparation example 1, comparative preparation example 7, and comparative preparation example 19 disclosed in table 9. Referring to table 9 and fig. 4, in the case where the total content (N1+ N2+ U1) of the near infrared ray absorbing pigments N1 and N2 and the ultraviolet ray absorbing pigment U1 is set to be in the range of 0 to 8.71 parts by weight, and the content of N1, N2 and U1 is changed so that the content ratio (U1/(N1+ N2)) of the ultraviolet ray absorbing pigment to the near infrared ray absorbing pigment is in the range of 0 to 4.94 weight ratio, it is known that the wavelength width W1 of the first transmission stop band can be adjusted to be in the range of 8.3nm to 35.4nm with the adjustment of the content of N1 and N2, and the wavelength width W2 of the second transmission stop band can be adjusted to be in the range of 10.0nm to 50.0nm with the adjustment of the content of U1. However, it is known that in the limited range where the total content (N1+ N2+ U1) is 4.78 to 8.71 parts by weight and the content ratio (U1/(N1+ N2)) is 0.70 to 4.94 parts by weight, when the OD2 value is 0.23 to 0.81, the first and second transmission inhibition bands are simultaneously formed, the wavelength width W1 of the first transmission inhibition band at this time is formed in the range of 8.3nm to 35.4nm, and the wavelength width W2 of the second transmission inhibition band is formed in the range of 27.8nm to 50.0 nm. In addition, it was found that the first transmission preventing tape and the second transmission preventing tape were not present when the near infrared absorbing dye was not contained or the ultraviolet absorbing dye was not contained.
Comparative preparation examples 20 to 38
Optical articles according to comparative production examples 20 to 38 were prepared by substantially the same method as that of production examples 7 to 12, except for the contents of the pigment for near infrared absorption N1 having a maximum absorption wavelength at 710 ± 5nm, the pigment for near infrared absorption N2 having a maximum absorption wavelength at 740 ± 5nm, and the pigment for ultraviolet absorption U1 having a maximum absorption wavelength at 380 ± 5 nm. In this case, the contents of the near-infrared absorbing dye and the ultraviolet absorbing dye are shown in table 10 below.
[ Table 10]
The wavelength widths W1 of the first transmission inhibition bands, the wavelength widths W2 of the second transmission inhibition bands, and the absorbance values of the optical articles according to comparative preparation examples 20 to 38 were calculated by substantially the same methods as the methods for measuring the transmittance and absorbance of the optical articles according to the preparation examples 1 to 6. The results are shown in Table 10. Referring to table 10, in the case where the total content (N1+ N2+ U1) of the near infrared ray absorbing pigments N1 and N2 and the ultraviolet ray absorbing pigment U1 is set to be in the range of 0 to 8.71 parts by weight, and the content of N1, N2 and U1 is changed so that the content ratio (U1/(N1+ N2)) of the ultraviolet ray absorbing pigment to the near infrared ray absorbing pigment is in the range of 0 to 5.29 weight ratio, it is known that the wavelength width W1 of the first transmission suppression band can be adjusted to be in the range of 8.6nm to 36.0nm as the content of N1 and N2 is adjusted, and the wavelength width W2 of the second transmission suppression band can be adjusted to be in the range of 10.5nm to 50.0nm as the content of U1 is adjusted. However, it is known that in the limited range where the total content (N1+ N2+ U1) is 4.92 to 8.71 parts by weight and the content ratio (U1/(N1+ N2)) is 0.75 to 5.29 parts by weight, when the OD2 value is 0.24 to 0.80, the first and second transmission inhibition bands are simultaneously formed, the wavelength width W1 of the first transmission inhibition band at this time is formed in the range of 8.6nm to 36.0nm, and the wavelength width W2 of the second transmission inhibition band is formed in the range of 33.1nm to 50.0 nm. In addition, it was found that the first transmission preventing tape and the second transmission preventing tape were not present when the near infrared absorbing dye was not contained or the ultraviolet absorbing dye was not contained.
Comparative preparation examples 39 to 57
Optical articles according to comparative production examples 39 to 57 were prepared by substantially the same method as that of production examples 13 to 18, except for the contents of the pigment for near infrared absorption N1 having a maximum absorption wavelength at 710 ± 5nm, the pigment for near infrared absorption N2 having a maximum absorption wavelength at 740 ± 5nm, and the pigment for ultraviolet absorption U1 having a maximum absorption wavelength at 380 ± 5 nm. In this case, the contents of the near-infrared absorbing dye and the ultraviolet absorbing dye are shown in table 11 below.
[ Table 11]
The wavelength widths W1 of the first transmission inhibition bands, the wavelength widths W2 of the second transmission inhibition bands, and the absorbance values of the optical articles according to comparative preparation examples 39 to 57 were calculated by substantially the same methods as the methods for measuring the transmittance and absorbance of the optical articles according to the preparation examples 1 to 6. The results are shown in Table 11. Referring to table 11, in the case where the total content (N1+ N2+ U1) of the near infrared ray absorbing pigments N1 and N2 and the ultraviolet ray absorbing pigment U1 was set to be in the range of 0 to 8.71 parts by weight, and the content of N1, N2 and U1 was changed so that the content ratio (U1/(N1+ N2)) of the ultraviolet ray absorbing pigment to the near infrared ray absorbing pigment was in the range of 0 to 5.53 weight ratio, it was found that the wavelength width W1 of the first transmission suppression band could be adjusted to be in the range of 10.0nm to 36.6nm with adjustment of the content of N1 and N2, and the wavelength width W2 of the second transmission suppression band could be adjusted to be in the range of 11.3nm to 50.0nm with adjustment of the content of U1. However, it is known that in the limited range where the total content (N1+ N2+ U1) is 5.11 to 8.71 parts by weight and the content ratio (U1/(N1+ N2)) is 0.82 to 5.53 parts by weight, when the OD2 value is 0.25 to 0.79, the first and second transmission prevention bands are simultaneously formed, the wavelength width W1 of the first transmission prevention band at this time is formed in the range of 10nm to 36.6nm, and the wavelength width W2 of the second transmission prevention band is formed in the range of 39.0nm to 50.0 nm. In addition, it was found that the first transmission preventing tape and the second transmission preventing tape were not present when the near infrared absorbing dye was not contained or the ultraviolet absorbing dye was not contained.
Comparative preparation examples 58 to 76
Optical articles according to comparative production examples 58 to 76 were prepared by substantially the same method as that of production examples 19 to 24, except that the contents of the pigment for near infrared absorption N1 having a maximum absorption wavelength at 710 ± 5nm, the pigment for near infrared absorption N2 having a maximum absorption wavelength at 740 ± 5nm, and the pigment for ultraviolet absorption U1 having a maximum absorption wavelength at 380 ± 5nm were changed. In this case, the contents of the near-infrared absorbing dye and the ultraviolet absorbing dye are shown in table 12 below.
[ Table 12]
The wavelength widths W1 of the first transmission inhibition bands, the wavelength widths W2 of the second transmission inhibition bands, and the absorbance values of the optical articles according to comparative preparation examples 58 to 76 were calculated by substantially the same methods as the methods for measuring the transmittance and absorbance of the optical articles according to the preparation examples 1 to 6. The results are shown in Table 12. Referring to table 12, in the case where the total content (N1+ N2+ U1) of the near infrared ray absorbing pigments N1 and N2 and the ultraviolet ray absorbing pigment U1 was set to be in the range of 0 to 8.71 parts by weight, and the content of N1, N2 and U1 was changed so that the content ratio (U1/(N1+ N2)) of the ultraviolet ray absorbing pigment to the near infrared ray absorbing pigment was in the range of 0 to 6.08 weight ratio, it was found that the wavelength width W1 of the first transmission suppression band could be adjusted to be in the range of 9.9nm to 37.1nm with adjustment of the content of N1 and N2, and the wavelength width W2 of the second transmission suppression band could be adjusted to be in the range of 9.4nm to 50.0nm with adjustment of the content of U1. However, it is known that in the limited range where the total content (N1+ N2+ U1) is 4.97 to 8.71 parts by weight and the content ratio (U1/(N1+ N2)) is 0.77 to 6.08 parts by weight, when the OD2 value is 0.24 to 0.79, the first and second transmission inhibition bands are simultaneously formed, the wavelength width W1 of the first transmission inhibition band at this time is formed in the range of 9.9nm to 37.1nm, and the wavelength width W2 of the second transmission inhibition band is formed in the range of 35.6nm to 50.0 nm. In addition, it was found that the first transmission preventing tape and the second transmission preventing tape were not present when the near infrared absorbing dye was not contained or the ultraviolet absorbing dye was not contained.
Comparative examples 1 to 76
Optical filters according to comparative examples 1 to 76 were prepared by substantially the same method as in examples 1 to 24, except that the optical articles prepared in comparative preparation examples 1 to 76 were used.
Experimental example 1
As described above, the optical article of the present invention may be provided with the pigment dispersion layer to provide the first transmission blocking tape and the second transmission blocking tape. As for the first transmission prevention band and the second transmission prevention band, it is known from various preparation examples and comparative preparation examples that the wavelength width and the presence or absence thereof are determined according to the content and content ratio of each of the near infrared ray absorbing pigment and the ultraviolet ray absorbing pigment and the OD2 value. Further, it can be seen that: in order to suppress a short wavelength shift of a visible light transmittance curve due to an increase in an incident angle of a light source and suppress a change in an integral value of the visible light transmittance curve to 1% or less even if the incident angle increases, it is necessary to appropriately overlap the transition region of the wavelength selective reflective layer provided on at least one surface of the optical article and a transmission stop band of the optical article, and the transmission stop band may have a wavelength width adjusted for overlapping.
In experimental example 1, the following experiment was performed in order to examine what kind of optical characteristics the spectral characteristics of the optical article of the present invention impart to the spectral characteristics of an optical filter including the optical article.
First, transmission spectra were measured at an incident angle of 0 degree using a spectrophotometer in a wavelength range of 300nm to 1200nm with respect to optical articles used in the optical filters prepared in examples 1 to 24 and comparative examples 1 to 76, respectively. From the obtained transmittance curve, the longest wavelength (λ _ cut-on) at which the transmittance reaches 50% in the wavelength region of 430nm or less and the shortest wavelength (λ _ cut-off) at which the transmittance reaches 50% in the wavelength region of 565nm or more are calculated. In addition, the visible light average transmittance for the wavelength range of 430nm to 565nm, the near infrared light average transmittance for the wavelength region of 800nm to 1200nm, and the transmittance at 1200nm were measured and shown in table 13. Further, fig. 7 to 10 show transmission spectra of the optical articles prepared in preparation example 3, preparation example 6, comparative preparation example 7, and comparative preparation example 19, respectively, measured according to the test samples.
Referring to table 13 and fig. 7 to 10, it can be seen that λ _ cut-on of the optical articles of production examples 1 to 24 having the first and second transmission-blocking bands exists in the range of 410nm to 420nm, and λ _ cut-off exists in the wavelength range of 625nm to 645 nm. Further, since the visible light average transmittance is also as high as 87% or more, when used in combination with a commonly used image sensor, a bright image in which the primary colors of the subject are sufficiently reproduced can be provided. In contrast, even when the optical articles of comparative preparation examples 1 to 76 do not have either one of the first and second transmission prevention bands, neither one of them, or both of them, since the wavelength width thereof is too wide, λ _ cut-on is excessively out of the range of 410nm to 420nm, λ _ cut-off is out of the range of 625nm to 645nm, or the visible light average transmittance is as low as 87% or less, it is difficult to obtain images of good quality when used in combination with a general-purpose image sensor.
Further, referring to table 13 and fig. 7 to 10, it is understood that the optical articles of production examples 1 to 24 and comparative production examples 1 to 76 have an average transmittance of 800nm to 1200nm of 25% or more and a transmittance of 1200nm of 50% or more. This result means that the transmittance of 800nm or more is not greatly affected by the presence or absence of the first and second transmission prevention bands, and is known to be mainly affected by the near-infrared-absorbing glass substrate.
Further, in the optical article having the first and second transmission stop bands of the present invention, in order to more precisely investigate short-wavelength shift in the second transmission stop band with an increase in incident angle of the light source, transmission spectra were measured in the range of 300nm to 1200nm using a spectrophotometer with respect to the optical articles related to preparation examples 1 to 24, respectively, at incident angle conditions of 0 degree and 40 degrees. From the obtained transmittance curve, the absolute value | λ _ T30% @0 ° - λ _ T30% @40 | of the difference between the wavelength λ _ T30% @0 ° at which the transmittance measured under the condition of the incident angle of 0 degrees in the wavelength region of 400nm to 410nm reaches 30% and the wavelength λ _ T30% @40 ° at which the transmittance measured under the condition of the incident angle of 40 degrees reaches 30% is calculated. The results are shown in Table 14. Referring to table 14, it can be seen that | λ _ T30% @0 ° - λ _ T30% @40 ° | values indicate values from 1.2nm to 1.8nm, and it can be confirmed that even if the incident angle increases to 40 degrees, as a measure of short wavelength shift, the shift value of the wavelength indicating 30% transmittance can be strictly controlled to 2nm or less.
[ Table 13]
[ Table 14]
Experimental example 2
In order to evaluate the short-wavelength shift of the visible light transmittance curve with the incident angle of the optical filter according to the present invention, the following experiment was performed.
First, the respective transmission spectra were measured at incident angles of 0 degrees and 40 degrees using a spectrophotometer in a wavelength range of 300nm to 1200nm for the optical filters of examples 1 to 24 and comparative examples 1 to 76, respectively. As an example of the measurement results thereof, fig. 11 to 14 show the measurement of the transmission spectra of the optical filters of example 3, example 6, comparative example 7, and comparative example 19, respectively.
From the transmittance curves obtained from the incident angles of 0 degree and 40 degrees, the integrated value for the transmittance for each wavelength is calculated, and the rate of change of the integrated value with the change of the incident angle is calculated by the following formula 2.
[ formula 2]
|(A-B)/A|*100
In the above formula 2, a represents an integrated value of transmittance measured under a condition of an incident angle of 0 degree in a wavelength range of 380nm to 780nm, and B represents an integrated value of transmittance measured under a condition of an incident angle of 40 degree in a wavelength range of 380nm to 780 nm.
In addition, from the transmittance curve measured under the condition of the incident angle of 0 degree, the shortest wavelength (λ _ cut-off) at which the transmittance reaches 50% in the wavelength region longer than 565nm and the visible light average transmittance for the wavelength range of 430nm to 565nm were calculated and shown in table 15.
[ Table 15]
Referring to table 15, even in the case where the optical articles of comparative preparation examples 1 to 76 were not provided with either one, neither, or both of the first and second transmission blocking tapes, since the wavelength width of one or both of the wavelength width W1 of the first transmission stop band or the wavelength width W2 of the second transmission stop band becomes excessively wide, W1 and W2 exceed 25nm and 45nm, respectively, and, since the optical filters comprising the optical articles of the comparative preparation examples 1 to 76 were 1% or more, even 7% or more, and therefore the difference in color sensation with the incident angle is liable to be caused remarkably, and even if suppressed to less than 1%, since the visible light average transmittance is reduced to a level of 91%, a problem may occur in that it is difficult to significantly distinguish images photographed in a low-illuminance photographing environment.
In contrast, it is known that optical filters comprising optical articles according to production examples 1 to 24 having a first transmission inhibition band with a wavelength width W1 of 5nm to 25nm and a second transmission inhibition band with a wavelength width W2 of 5nm to 45nm and an OD2 of 0.2 to 0.4, the difference in the integrated value is suppressed within 1% because the short-wavelength shift of the visible light transmittance curve is suppressed, and the visible light average transmittance shows excellent characteristics of 93% or more, even when the incident angle is increased from 0 degree to 40 degrees. Meanwhile, λ _ cut-off is also in the range of 630nm to 655nm, and thus when used in combination with a general image sensor, primary colors can be sufficiently reproduced.
Claims (14)
1. An optical article, comprising:
a near-infrared ray absorption glass substrate containing divalent copper ions as a coloring component, having an average transmittance of 90% or more in a wavelength region of 430nm to 565nm, and having a shortest wavelength at which the transmittance reaches 50% in a wavelength region having a wavelength longer than 565nm occurring in 660nm to 690 nm; and
a pigment dispersion layer formed on one or both surfaces of the near-infrared-absorbing glass substrate, in which a near-infrared-absorbing pigment and an ultraviolet-absorbing pigment are dispersed in a resin matrix,
when the transmittance curve of the optical article is measured at an incident angle of 0 degree using a spectrophotometer in a wavelength range of 300nm to 1200nm, the optical article has a first transmittance blocking band having a transmittance of 1% or less in a wavelength region of 690nm to 730nm and a second transmittance blocking band having a transmittance of 25% or less in a wavelength region of 360nm to 410nm,
the optical article satisfies the following conditions (I) to (II):
(I) a wavelength width (W1) of the first transmission rejection band is 5nm to 25 nm;
(II) the second transmission-blocking band has a wavelength width (W2) of 5nm to 45 nm;
and wherein the first and second electrodes are, among others,
in the case where the absorbance curve of the optical article is measured with a spectrophotometer at an incident angle of 0 degree in a wavelength range of 300nm to 1200nm, when the maximum value of absorbance is normalized to 1 in the wavelength region of the first transmission inhibition band, the maximum value OD2 of absorbance in the wavelength region of the second transmission inhibition band satisfies the following condition of formula 1:
[ formula 1]
0.2≤OD2≤0.4。
2. The optical article of claim 1,
when a transmittance curve of the optical article is measured at an incident angle of 0 degree using a spectrophotometer in a wavelength range of 300nm to 1200nm, the longest wavelength at which transmittance reaches 50% in a wavelength region having a wavelength shorter than 430nm exists in a wavelength region of 410nm to 420nm,
the shortest wavelength at which the transmittance reaches 50% in a wavelength region having a wavelength longer than 565nm exists in a wavelength region of 625nm to 645 nm.
3. The optical article of claim 1,
when the transmittance curve of the optical article is measured at an incident angle of 0 degree with a spectrophotometer in a wavelength range of 300nm to 1200nm, the average transmittance in a wavelength region of 430nm to 565nm is 87% or more.
4. The optical article of claim 1,
when the transmittance curve of the optical article is measured with a spectrophotometer at an incident angle of 0 degree in a wavelength range of 300nm to 1200nm, the average transmittance in a wavelength region of 800nm to 1200nm is 25% or more, and the transmittance at a wavelength of 1200nm is 50% or more.
5. The optical article of claim 1,
when the transmittance curve of the optical article is measured with a spectrophotometer at the conditions of incident angles of 0 degree and 40 degree in the wavelength range of 300nm to 1200nm, respectively, the absolute value of the difference between the wavelength at which the transmittance reaches 30% measured at the conditions of incident angles of 0 degree in the wavelength region of 400nm to 410nm and the wavelength at which the transmittance reaches 30% measured at the conditions of incident angles of 40 degree is 2nm or less.
6. The optical article of claim 1,
the dye for near infrared absorption has a maximum absorption wavelength in a range of 690nm to 750nm, and the dye for ultraviolet absorption has a maximum absorption wavelength in a range of 350nm to 410nm, and includes any one or more of compounds represented by the following chemical formula 1 and chemical formula 2:
[ chemical formula 1]
[ chemical formula 2]
In the chemical formula 1, the metal oxide is represented by,
a represents an aminophenyl group, an indolylmethylene group, or an indolinyl group,
has two A to
Is a structure in which centers are bonded to each other,
any one or more of hydrogen atoms present in the aminophenyl, indolylmethylene or indolinyl group represents, independently of one another, hydrogen, halogen, hydroxyl, cyano, nitro, carboxyl, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a sulfonamide group, or an amide group which is substituted or unsubstituted with an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms or an aralkyl group having 7 to 20 carbon atoms;
the chemical formula 1 is any one of compounds represented by the following chemical formula 1a to chemical formula 1c,
[ chemical formula 1a ]
[ chemical formula 1b ]
[ chemical formula 1c ]
In the chemical formulas 1a to 1c, a1, a2, and a3 represent, independently of each other, hydrogen, halogen, hydroxyl, cyano, nitro, carboxyl, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a sulfonamide group, or an amide group substituted or unsubstituted with an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms,
in the chemical formula 2, R1 to R3 are each independently represented by hydrogen, cyano group, amino group, or the following chemical formula 2-a,
[ chemical formula 2-a ]
In chemical formula 2-a, b1 represents independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms,
r4 is represented by hydrogen, cyano or the following chemical formula 2-b,
[ chemical formula 2-b ]
In chemical formula 2-b, b2 represents hydrogen, an alkyl group having 1 to 18 carbon atoms, or an amino group,
one or more hydrogens of R1 to R4 of chemical formula 2 are each independently substituted or unsubstituted with one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, a halogen, a cyano group, a nitro group, a hydroxyl group, and a carboxyl group.
7. The optical article of claim 1,
the total content of the pigment for near infrared ray absorption and the pigment for ultraviolet ray absorption is in the range of 2.5 to 5.5 parts by weight when the content of the pigment dispersion layer is 100 parts by weight.
8. The optical article of claim 1,
the content ratio of the ultraviolet absorbing dye to the near-infrared absorbing dye in the dye dispersion layer is in the range of 0.5 to 3.0 by weight.
9. The optical article of claim 1,
the thickness of the near infrared ray absorption glass substrate is 0.140mm to 0.220 mm.
10. The optical article of claim 1,
the polymer resin constituting the resin matrix includes at least one selected from the group consisting of polyester resins, polycarbonate resins, acrylic resins, polyolefin resins, cycloolefin resins, polyimide resins, polyamide resins, and polyurethane resins.
11. An optical filter comprising:
the optical article of any one of claims 1 to 10;
a first wavelength selective reflective layer formed on one side of the optical article; and
a second wavelength selective reflective layer formed on the other side of the optical article,
the optical filter is an optical filter satisfying the following formula 2:
[ formula 2]
|（X-Y）/X|*100≤1%
In the formula 2, X represents an integrated value of the transmittance when a transmittance curve of the optical filter is measured at an incident angle of 0 degree using a spectrophotometer in a wavelength range of 380nm to 780nm,
y represents an integrated value of the transmittance when the transmittance curve of the optical filter is measured at an incident angle of 40 degrees with a spectrophotometer in a wavelength range of 380nm to 780 nm.
12. The optical filter of claim 11,
when the transmittance curve of the optical filter is measured at an incident angle of 0 degree using a spectrophotometer in a wavelength range of 300nm to 1200nm, the shortest wavelength of the optical filter, at which transmittance reaches 50% in a wavelength region having a wavelength longer than 565nm, appears in 630nm to 655 nm.
13. The optical filter of claim 11,
when the transmittance curve of the optical filter is measured at an incident angle of 0 degree using a spectrophotometer in a wavelength range of 300nm to 1200nm, the average transmittance in a wavelength region of 430nm to 565nm is 93% or more.
14. A photographing apparatus comprising the optical filter of any one of claims 11 to 13.
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| PCT/KR2018/011206 WO2019066398A2 (en) | 2017-09-28 | 2018-09-21 | Optical product and optical filter including same |
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| KR102514588B1 (en) * | 2019-12-23 | 2023-03-27 | 주식회사 엘엠에스 | Near-infrared ray absorbing article and Optical apparatus comprising the same |
| JP2021099481A (en) * | 2019-12-23 | 2021-07-01 | エルエムエス・カンパニー・リミテッドＬＭＳ Ｃｏ．，Ｌｔｄ． | Near-infrared absorbing plate and optical device comprising the same |
| KR102519358B1 (en) * | 2020-06-05 | 2023-04-11 | 주식회사 엘엠에스 | Near-infrared ray absorbing article and an Optical apparatus comprising the same |
| JP2021192089A (en) * | 2020-06-05 | 2021-12-16 | エルエムエス・カンパニー・リミテッドLMS Co., Ltd. | Near-infrared absorption plate and optical device including the same |
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| JP4514577B2 (en) | 2004-10-21 | 2010-07-28 | 大阪瓦斯株式会社 | Infrared absorption filter and infrared absorption panel |
| CN101881850A (en) | 2010-06-24 | 2010-11-10 | 四川长虹电器股份有限公司 | Display optical filter with anti-electromagnetic radiation and filtering functions and display using same |
| WO2013038938A1 (en) | 2011-09-15 | 2013-03-21 | Jsr株式会社 | Near-infrared cut filter and device including near-infrared cut filter |
| WO2013054864A1 (en) | 2011-10-14 | 2013-04-18 | Jsr株式会社 | Optical filter, solid state image-capturing device using same, and camera module using same |
| WO2013183557A1 (en) | 2012-06-04 | 2013-12-12 | 旭硝子株式会社 | Near infrared cut-off filter |
| KR101377201B1 (en) | 2013-03-25 | 2014-03-25 | 주식회사 엘지화학 | Optical film exhibiting excellent blocking property for ultraviolet rays and polarizing plate comprising the same |
| JP6443329B2 (en) | 2013-04-10 | 2018-12-26 | Ａｇｃ株式会社 | Infrared shielding filter and imaging device |
| JP6103152B2 (en) * | 2015-01-14 | 2017-03-29 | 旭硝子株式会社 | Near-infrared cut filter and solid-state imaging device |
| CN106062592B (en) | 2015-01-14 | 2018-11-23 | Ａｇｃ株式会社 | Near infrared ray cut-off filter and photographic device |
| JP2017146506A (en) | 2016-02-18 | 2017-08-24 | 旭硝子株式会社 | Optical filter and imaging apparatus |
| WO2017146413A2 (en) | 2016-02-24 | 2017-08-31 | 주식회사 엘엠에스 | Optical article and optical filter comprising same |
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2018
- 2018-09-21 US US16/651,789 patent/US11698480B2/en active Active
- 2018-09-21 WO PCT/KR2018/011206 patent/WO2019066398A2/en active Application Filing
- 2018-09-21 CN CN201880060716.7A patent/CN111108414B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| KR101931731B1 (en) | 2018-12-24 |
| WO2019066398A2 (en) | 2019-04-04 |
| CN111108414A (en) | 2020-05-05 |
| US20200241185A1 (en) | 2020-07-30 |
| WO2019066398A3 (en) | 2019-05-23 |
| US11698480B2 (en) | 2023-07-11 |
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